US12068463B2 - Method of enhancing electrochemical cell performance - Google Patents
Method of enhancing electrochemical cell performance Download PDFInfo
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- US12068463B2 US12068463B2 US17/420,832 US202017420832A US12068463B2 US 12068463 B2 US12068463 B2 US 12068463B2 US 202017420832 A US202017420832 A US 202017420832A US 12068463 B2 US12068463 B2 US 12068463B2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/02—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries for charging batteries from AC mains by converters
- H02J7/04—Regulation of charging current or voltage
- H02J7/12—Regulation of charging current or voltage using magnetic devices having controllable degree of saturation, i.e. transductors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to the performance of electrochemical cells and particularly, although not exclusively, to increasing the speed of charge and discharge and the capacity of electrochemical cells.
- Electrochemical cells are vital to many electrical systems, in particular portable devices such as mobile phones and laptops and, increasingly, electric vehicles.
- the portability of electronic devices/vehicles are dependent on the performance of their cells. In general it is desirable to have a cell that has a large capacity and a short charging time to increase the ratio of time that the devices/vehicles can operate independently of an external power source to time that they must be connected to an external power source for charging.
- electrochemical cells can be selected based on size, shape, voltage, current and other requirements. Examples of common shapes of cells are pouch cells, cylindrical cells, Swagelok cells and coin cells. The cells may also be connected in a battery to provide the appropriate voltage and/or current for the application.
- a common method of quickly charging a cell while avoiding over-charging is to supply a constant current in a first charging phase until a predetermined voltage is reached in the cell and then, in a second charging phase, holding the voltage constant while the current decays to ensure the cell reaches capacity.
- the first charging phase quickly increases the charge in the cell and the second charging phase is slower.
- a C-rate is a measure of the rate of charge or discharge of a cell and is the current divided by the capacity and with units of per hour.
- the present invention has been devised in light of the above considerations.
- the present invention provides a method of enhancing performance of an electrochemical cell having a first electrode and a second electrode and electrolyte between the first and second electrodes, the first and second electrodes defining a current flow path, the method comprising providing a changing magnetic field through the cell.
- the changing magnetic field aids ion transport in the electrochemical cell thereby meaning that performance of the battery is enhanced.
- the cell may include a separator between the electrodes.
- the transport of ions can be improved in the electrolyte and/or in the electrodes and/or in the separator.
- the changing magnetic field through the cell means that the magnetic flux in the cell varies over time in magnitude and/or direction and/or distribution.
- One characteristic of the cell which can be enhanced using the above method is the speed of charging of the cell. Ion transport in cells is often the rate determining process during charging and so aiding the transport of ions speeds up charging of the cell. Another characteristic of the cell which can be enhanced using the above method is the speed of discharging as ion transport is improved in an analogous way to during charging. Another characteristic of the cell which can be enhanced using the above method is the capacity of the cell. This may be achieved by performing the method above on the cell during formation of the cell or during operation.
- the changing magnetic field may be a rotating magnetic field and/or an oscillating magnetic field and/or a pulsing magnetic field.
- the changing magnetic field may have a direction with a component perpendicular to the current flow path.
- the changing magnetic field may have a direction with a component parallel to the current flow path.
- Rotation of the magnetic field may be around an axis having a component perpendicular to a direction of the magnetic field.
- the rotation of the magnetic field may be around an axis having a component parallel to a direction of the magnetic field.
- Rotation of the magnetic field may be around an axis having a component perpendicular to a direction of the current flow path.
- the rotation of the magnetic field may be around an axis having a component parallel to a direction of the current flow path.
- the rotating magnetic field may be provided by a spinning permanent magnet, or a temporary magnet, or electromagnet or may be provided by an array of electromagnets which are sequentially activated to effectively rotate the magnetic field.
- the electrochemical cell may be a battery.
- the battery may be a coin cell, a cylindrical cell, a prismatic cell or a pouch cell.
- the battery may be a positive ion battery and the current flow path may be the direction of travel of positive ions.
- the battery may be a lithium-ion battery.
- the battery may be a negative ion battery and the current flow path may be the direction of travel of negative ions.
- the cell may be for powering an electric vehicle, a mobile phone, a laptop computer, tablet or other portable or stationary device.
- the cell may be a fuel cell.
- the electrochemical cell may be part of an array of two or more cells.
- the magnetic field may be provided by a permanent magnet or temporary magnet or an electromagnet.
- the electrolyte may be a solid, liquid or a gel.
- the electrolyte may be non-aqueous including organic electrolytes.
- a magnetic field generator may be provided for generating the changing magnetic field.
- the magnetic field generator may be within the cell or external to the cell.
- the present invention provides a charge accelerator for enhancing performance of an electrochemical cell, the device being configured to carry out a method of enhancing performance of an electrochemical cell described above.
- the present invention provides a method of charging an electrochemical cell comprising the steps of providing a current or voltage to the cell from a power source whilst performing a method of enhancing performance of an electrochemical cell described above.
- charging a cell includes moving ions in a cell whether imposed by a current or voltage or by spontaneous movement of the ions.
- the present invention provides a method of discharging an electrochemical cell comprising the steps of extracting a current or voltage from the cell whilst performing a method of enhancing performance of an electrochemical cell described above.
- the present invention provides a method of enhancing capacity of an electrochemical cell comprising the steps of forming or during operation of an electrochemical cell whilst performing a method of enhancing performance of an electrochemical cell described above.
- the invention includes the combination of the aspects and preferred features described except where such a combination is clearly impermissible or expressly avoided.
- FIG. 1 shows a side view of an example arrangement of equipment used in enhancing the performance of a cell.
- FIG. 2 shows a diagram of an example arrangement used to enhance the performance of a pouch cell.
- FIG. 2 A shows a cross-sectional side view and FIG. 2 B shows a top view.
- FIG. 3 shows capacity of a cell over time of a pouch cell when charged from 3.4 V to 4.2 V at 0.841 A until 4.2 V was reached then held at constant voltage while the current decays and capacity is reached (i) with a changing magnetic field (dashed line) and (ii) with a permanent magnetic field (solid line).
- FIG. 4 shows current and voltage over time of the pouch cell charged from 3.4 V to 4.2 V at 0.841 A until 4.2 V was reached then held at constant voltage while the current decays and capacity is reached (i) with a rotating magnetic field present (dashed line) and (ii) with a permanent magnetic field (solid line).
- FIG. 5 shows capacity of a cell over time of the pouch cell when charged from 3.4 V to 4.2 V at 0.841 A until 4.2 V was reached then held at constant voltage while the current decays and capacity is reached (i) with a rotating magnetic field present (dashed line) and (ii) with a permanent magnetic field (solid line).
- FIG. 6 shows the speed of charging of a 400 mAh pouch cell in cycles with a rotating magnetic field and with a permanent a magnetic field.
- FIG. 7 shows the time taken to charge the 400 mAh pouch cell of FIG. 6 with a rotating magnetic field and with a permanent a magnetic field along with dimensions and properties of the cell used.
- FIG. 8 shows the speed of charging of a 200 mAh pouch cell at 4C with a rotating magnetic field and with a permanent a magnetic field.
- FIG. 9 shows the time taken to charge the 200 mAh pouch cell of FIG. 8 with a rotating magnetic field and with a permanent a magnetic field at 4C along with dimensions and properties of the cell used.
- FIG. 10 shows a diagram of an example arrangement used to enhance the performance of a Swagelok-type cell.
- FIG. 10 A shows a cross-sectional side view and
- FIG. 10 B shows a top view.
- FIG. 11 shows the speed of charging at 1C, 2C and 3C performed on a LMO/Graphite Swagelok cell with a rotating magnetic field and with a permanent a magnetic field.
- FIG. 12 shows the time taken to charge the LMO/Graphite Swagelok cell of FIG. 11 with a rotating magnetic field and with a permanent magnetic field at 1C, 2C and 3C along with the dimensions of the cell used.
- FIG. 13 shows a diagram of an example arrangement used to enhance the performance of a cylindrical-type cell.
- FIG. 13 A shows a cross-sectional view along line A-A
- FIG. 13 B shows a cross-sectional side view along line B-B
- FIG. 13 C shows a top view.
- FIG. 14 shows the speed of charging of a cylindrical 2190 mAh LG 18650 cell in cycles with a rotating magnetic field and the cell oriented in two directions 90 degrees apart from one another and with a permanent a magnetic field.
- FIG. 15 shows the time taken to charge the cylindrical 2190 mAh LG 18650 cell of FIG. 14 with a rotating magnetic field and the cell oriented in two directions 90 degrees apart from one another and with a permanent a magnetic field.
- the arrangement of equipment shown in FIG. 1 can be used to enhance and monitor the performance of a cell 1 while charging or discharging.
- the cell 1 is located on top of a rotating magnetic field generator 2 .
- the cell 1 is connected to the potentiostat and computer 3 via terminals 4 .
- the potentiostat controls the potential across the cell 1 and may charge or discharge the cell 1 .
- the computer monitors the current, and/or capacity and/or voltage of the cell 1 .
- the rotating magnetic field generator 2 provides a rotating magnetic field through the cell 1 .
- This arrangement can be used for testing the cell, but when monitoring of the cell 1 is not required, the potentiostat, computer 3 and terminals 4 can be removed and optionally replaced by a power source or drain for charging or discharging the cell.
- the cell 1 is located on top of the rotating magnetic field generator 2 , but in other embodiments of the invention, the cell 1 and rotating magnetic field generator 2 may be oriented differently as long as the rotating magnetic field generator 2 can produce a magnetic field through the cell 1 .
- the rotation of the magnetic field may be around an axis substantially parallel to the direction of the magnetic field produced.
- the direction of the magnetic field produced in the cell 1 may be substantially parallel to a direction between the magnetic field generator 2 and the cell 1 and the rotation of the field may be around an axis parallel to a direction between the magnetic field generator 2 and the cell 1 as shown in FIGS. 2 A and 2 B .
- the rotation magnetic field may be around an axis substantially perpendicular to the direction of the magnetic field produced.
- the direction of the magnetic field produced in the cell 1 may be substantially perpendicular to a direction between the magnetic field generator 2 and the cell 1 and the rotation of the field may be around an axis parallel to a direction between the magnetic field generator 2 and the cell 1 .
- the rotating magnetic field generator 2 in the arrangement of FIG. 1 may be replaced with a changing magnetic field generator that produces a changing magnetic field that varies in another way.
- a changing magnetic field generator may be used in to produce a magnetic field that rotates and/or oscillates and/or pulses.
- the term “under field conditions” refers to the presence of a changing magnetic field.
- results for charging the cells in the presence of a changing magnetic field are shown along with comparative examples of the cells in the absence of a changing magnetic field.
- the arrangements used in the examples and in the comparative examples differ only in that the magnetic field provided in the comparative examples is constant in direction and magnitude, whereas the magnetic field provided in the examples is changing.
- FIG. 2 shows an arrangement used to enhance performance of a pouch cell 11 .
- the magnetic field generator 12 produces a magnetic field having a direction parallel to the direction shown by the arrow in FIG. 2 A .
- the magnetic field produced rotates in the direction shown by the arrow in FIG. 2 B .
- the magnetic field passes through pouch cell 11 .
- the magnetic field be offset from the axis of rotation to ensure that the magnetic flux in the cell changes over time.
- the magnetic field generator 12 is an electromagnet powered by power supply 15 .
- Potentiostat 13 is connected to the pouch cell 11 and controls the potential over the cell and can be used to charge or discharge the cell.
- the pouch cell 11 is formed of a first electrode and a second electrode separated from one another by an electrolyte.
- the electrodes are substantially parallel and extend across a length and width of the cell.
- the pouch cell 11 has contacts for each of the electrodes which may be connected to a potentiostat as shown in FIG. 2 .
- the pouch cell 11 is oriented so that the direction of the magnetic field passes through the first electrode of the cell, through the electrolyte and through the second electrode.
- the direction of the magnetic field is parallel to the direction of a current path between the electrodes.
- the rotation plane of the magnetic field is parallel to the planes of the electrodes.
- FIG. 3 shows the capacity of pouch cell 11 when charged in the presence of a magnetic field produced by the magnetic field generator 12 when the field is (i) rotating (shown by the dashed line) and (ii) not rotating (shown by the solid line).
- the pouch cell 11 was charged in two phases. In the first phase, the cell was charged from 3.4V to 4.2V at 0.841 A until 4.2V was reached and then in the second phase, the cell was held at constant voltage while the current decayed and capacity was reached.
- the first phase where a constant current is applied to the cell can be seen by the horizontal line portions of the current graph in FIG. 4 .
- the second phase where voltage is held constant and current decays while full capacity is reached can be seen where the current changes.
- a magnetic field was produced by an electromagnet in the magnetic field generator 12 .
- the electromagnet was spun at 1160 rpm. The results show that the time taken to charge the cell was reduced by 68% by the presence of the rotating magnetic field.
- FIG. 4 shows the current and voltage during the charging of the pouch cell 11 in the conditions described in relation to FIG. 3 .
- the dashed line shows the charge when the magnetic field is rotating and the solid line shows charging when the magnetic field is not rotating (it is constant).
- the graphs show that, in the presence of a rotating magnetic field, the time taken to reach the voltage of 4.2V is increased so that the first phase of charging where current is applied is maintained for a longer period. As the first phase of charging increases the charge held by the cell more quickly than the second phase, this means that charging overall is quicker when the rotating magnetic field is present through the cell.
- FIG. 5 shows the capacity of the pouch cell 11 when charged in the presence of a magnetic field produced by magnetic field generator 12 when the field is (i) rotating (shown by the dashed line) and (ii) not rotating (shown by the solid line).
- the pouch cell 11 was charged in two phases. In the first phase, the cell was charged from 3.4V to 4.2V at 0.841 A until 4.2V was reached and then in the second phase, the cell was held at constant voltage while the current decayed and capacity was reached.
- FIG. 6 shows results of testing a pouch cell 21 .
- the pouch cell 21 has a 400 mAh capacity and has dimensions of 5 cm by 2 cm by 0.5 cm.
- the pouch cell 21 is commercially available via the part information: +PL-402248-2C, 3.7V 400 mAh ⁇ PO 7006 20140726.
- the rate of charge of the pouch cell 21 is shown in FIG. 6 for nine charge cycles. Cycles 1 to 3, 7 and 8 were in the presence of a magnetic field rotating at 1170 rpm and cycle 9 was in the presence of the magnetic field rotating at 1000 rpm. Cycles 4 to 6 were in the presence of a static magnetic field.
- the rate of charging was consistently increased by the rotation of the magnetic field by around 15%.
- FIG. 7 shows the time taken to charge pouch cell 21 in eight charge cycles with a rotating field at 1170 rpm, a rotating field at 1000 rpm, and a static magnetic field (labelled ‘no field’ in the figure). As can be seen in FIG. 7 , the time taken to charge the cell is consistently decreased by around 15% in the presence of a rotating magnetic field.
- FIG. 8 shows results of testing a pouch cell 31 .
- the pouch cell 31 has a 200 mAh capacity and has dimensions of 2.5 cm by 1.7 cm by 0.5 cm.
- the pouch cell 31 is commercially available via the part information: ⁇ PL-651628-2C, 3.7V 210 mAh +PO 7994.
- the rate of charge of the pouch cell 31 is shown in FIG. 8 for two charge cycles.
- the first cycle was in the presence of a magnetic field rotating at 1160 rpm and the second cycle was in the presence of a static magnetic field.
- FIG. 9 shows the time taken to charge pouch cell 31 in a charge cycle with a rotating field at 1160 rpm, and a static magnetic field (labelled ‘no field’ in the figure). As can be seen in FIG. 9 , the time taken to charge the cell at 4C is decreased by 58% in the presence of a rotating magnetic field.
- FIG. 10 shows an arrangement used to enhance performance of a Swagelok-type cell 41 .
- the magnetic field generator 42 produces a magnetic field having the direction parallel to the direction shown by the arrow in FIG. 10 A .
- the magnetic field produced rotates in the direction shown by the arrow in FIG. 10 B .
- the magnetic field passes through Swagelok cell 41 .
- the magnetic field be offset from the axis of rotation to ensure that the magnetic flux in the cell changes over time.
- the magnetic field generator 42 is an electromagnet powered by power supply 45 .
- Potentiostat 43 is connected to the Swagelok cell 41 and controls the potential over the cell and can be used to charge the cell.
- the Swagelok cell 41 is formed of a first electrode and a second electrode separated from one another by an electrolyte and separator material.
- the electrodes are substantially parallel and extend across a length and width of the cell.
- the Swagelok cell 41 has contacts for each of the electrodes which may be connected to a potentiostat as shown in FIG. 10 .
- the Swagelok cell 41 is oriented so that the direction of the magnetic field passes through the cell, perpendicularly to the direction of a current path between the electrodes.
- the rotation plane of the magnetic field is perpendicular to the planes of the electrodes.
- FIG. 11 shows results of testing Swagelok cell 51 .
- the Swagelok cell 51 has dimensions of 5 cm by 2.5 cm.
- the Swagelok cell 51 is commercially available as a LMO/Graphite Swagelok cell.
- the rate of charge of the Swagelok cell 51 is shown in FIG. 11 for charge cycles at 1C, 2C and 3C, each in the presence of a rotating magnetic field and in the presence of a static magnetic field (labelled as no field in the figure).
- the rotating magnetic field had a speed of 1100 rpm.
- FIG. 12 shows the time taken to charge Swagelok cell 51 in charge cycles at 1C, 2C and 3C, each in the presence of a rotating magnetic field and in the presence of a static magnetic field (labelled as no field in the figure). As can be seen in FIG. 12 , the time taken to charge the cell 51 is consistently decreased in the presence of a rotating magnetic field.
- FIG. 13 shows an arrangement used to enhance performance of a cylindrical cell 61 .
- the magnetic field generator 62 produces a magnetic field having the direction parallel to the direction shown by the arrow in FIG. 13 B .
- the magnetic field produced rotates in the direction shown by the arrow in FIG. 13 C .
- the magnetic field passes through cylindrical cell 61 .
- the cylindrical cell 61 is formed of a first electrode and a second electrode separated from one another by an electrolyte.
- the electrodes are rolled into a spiral configuration and extend across a length of the cell.
- the cylindrical cell 61 has contacts for each of the electrodes which may be connected to a potentiostat as shown in FIG. 13 .
- the cylindrical cell 61 is oriented in FIG. 13 so that the direction of the magnetic field passes through the cross-section of the cylindrical shape, perpendicularly to a direction between the flat ends of the cylindrical shape.
- the rotation plane of the magnetic field is perpendicular to the planes of the end faces of the cylindrical cell.
- the cylindrical cell may alternatively be oriented so that the direction of the magnetic field passes through the ends of the cylindrical cell.
- the magnetic field be offset from the axis of rotation to ensure that the magnetic flux in the cell changes over time.
- the magnetic field generator 62 is an electromagnet powered by power supply 65 .
- Potentiostat 63 is connected to the cylindrical cell 61 and controls the potential over the cell and can be used to charge the cell.
- FIG. 14 shows results of testing cylindrical cell 71 .
- the cylindrical cell 71 has dimensions of 6.5 cm by 1.8 cm.
- the cylindrical cell 51 is commercially available as a cylindrical 2190 mAh LG 18650 cell.
- the rate of charge of the cylindrical cell 71 is shown in FIG. 14 for six charge cycles. Cycles 1 and 2 were in the presence of a magnetic field rotating at 1170 rpm, cycle 5 was in the presence of the magnetic field rotating at 1500 rpm and cycle 6 was in the presence of a magnetic field rotating at 1200 rpm. Cycles 3 and 4 were in the presence of a static magnetic field. In cycles 5 and 6, the cylindrical cell was positioned so at an orientation 90 degrees from the position shown in FIG. 13 A so that a flat end of the cell faces the magnetic field generator 62 .
- the rate of charging was generally higher in the presence of a rotating magnetic field.
- FIG. 15 shows the time taken to charge cylindrical cell 71 in the charge cycles of FIG. 14 .
- the time taken to charge the cell 71 was generally lower in the presence of a rotating magnetic field.
- the ion velocity, v, within a liquid electrolyte will increase until overcome by drag forces, F D .
- the electric field force, F E which drives the motion of the ion can be described by:
- Equating the electric and drag forces determines the terminal velocity of the ion, thus mobility, u i :
- u i ⁇ " ⁇ [LeftBracketingBar]”
- z i ⁇ " ⁇ [RightBracketingBar]” ⁇ q 6 ⁇ ⁇ ⁇ r eq . 4
- the mobility influences the conductivity through the equation: ⁇ i (
- the Ohmic resistance, ⁇ can be described by:
- the magnetic field influences the activation energy as: B ⁇ E ⁇ F E ⁇ u i ⁇ i ⁇ exp( ⁇ G act ) eq. 11
- ⁇ i 1 ⁇ i ⁇ ⁇ ohmic eq . 12
- the magnetic field can be produced using a permanent magnet or an electromagnet.
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Secondary Cells (AREA)
- Charge And Discharge Circuits For Batteries Or The Like (AREA)
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Abstract
Description
-
- zi charge number of the ion
- q fundamental charge of an electron (1.6×10−19C)
- dV voltage differential
- dx spatial differential
F D=6πμrv eq. 2
-
- μ viscosity of the liquid
- r radius of the ion
- v velocity of the ion
σi(|z i |F)c i u i eq. 5
-
- ci molar concertation
F z ∝u i∝σi eq. 6
-
- ΔGact activation energy
- F Faraday constant
- k Boltzman constant
- T Temperature
F E ∝u i∝σi∝exp(−ΔG act) eq. 8
-
- ∇ Curl operator (infinitesimal rotation of a 3-dimensional vector field)
- r position
- t time
F E =qE eq. 10
B∝E∝F E ∝u i∝σi∝exp(−ΔG act) eq. 11
B∝η ohmic eq. 13
-
- B magnetic induction
- A cross-sectional area of plunger
- μ0 permeability of space
-
- C proportionality constant
- A cross-sectional area of plunger
- n number of turns in the solenoid
- I current
- l length of the solenoid
Claims (14)
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GB2617438B (en) * | 2023-01-27 | 2024-05-01 | Gaussion Ltd | Magnetic flux generator |
GB2628591B (en) * | 2023-03-29 | 2025-06-11 | Gaussion Ltd | Apparatus for use with electrochemical cells |
GB2628585B (en) * | 2023-03-29 | 2025-06-04 | Gaussion Ltd | Magnetic flux generator |
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US20220093981A1 (en) | 2022-03-24 |
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CN113302779A (en) | 2021-08-24 |
CN113302779B (en) | 2024-10-01 |
EP4167343B1 (en) | 2025-03-12 |
EP3909092A1 (en) | 2021-11-17 |
JP7576146B2 (en) | 2024-10-30 |
JP2025020174A (en) | 2025-02-12 |
JP2022515678A (en) | 2022-02-21 |
EP3909092C0 (en) | 2024-04-03 |
JP7399170B2 (en) | 2023-12-15 |
ES2980369T3 (en) | 2024-10-01 |
EP4167343A1 (en) | 2023-04-19 |
EP3909092B1 (en) | 2024-04-03 |
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